CN108017598B - Epoxy butane composition and preparation method thereof - Google Patents
Epoxy butane composition and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to an epoxybutane composition and a process for preparing the same, comprising at least 99.6 wt.% epoxybutane and less than 2500wppm epoxyisobutane. Mainly solves the problems of long separation flow, limited yield and low purity of the butylene oxide through producing a small amount of butylene oxide as a byproduct of propylene oxide production, and discloses a butylene oxide composition, in particular a butylene oxide composition produced by a CHP method, which has the advantages of wide raw material source, low cost, high purity of polymer products such as polyether polyol, foaming agent and the like, and green and environment-friendly process when used for producing the polymers such as polyether polyol, foaming agent and the like; can be used for producing polyether polyols and foaming agents.
Description
Technical Field
The invention relates to an epoxy butane composition and a preparation method thereof, in particular to an epoxy butane composition which is obtained by carrying out epoxidation reaction on a catalyst containing mesoporous or macroporous silicon dioxide by using cumene hydroperoxide as an oxidant.
Background
Butylene Oxide (BO) is an important organic compound and can be used for preparing organic synthesis intermediates and polyether polyol to produce 1, 2-butanediol, butanol amine and the like; can also be used as a foaming agent, a thinner of nitrolacquer, an antioxidant of chlorine-containing compounds, and the like; it can also be used as a stabilizer for chlorinated solutions. The production routes for BO are mainly chlorohydrin process and epoxidation process. The epoxidation method is classified into a hydrogen peroxide cumene method (CHP method) and a hydrogen peroxide oxidation method (HPPO method).
Industrially, butylene oxide is mainly recovered from a by-product of propylene oxide production. During the process of producing ethylene oxide and propylene oxide by using cracking tail gas through hypochlorination, the residue of a propylene oxide tower can be obtained, wherein the content of butylene oxide is as high as 74.6%, and a small amount of propylene oxide, ethylene oxide, water and high-boiling residues are also obtained. After distillation, condensation and water removal, a finished product of the butylene oxide with the content of about 87 percent can be obtained. However, the method has long process flow, low product purity and relatively low yield. The chlorohydrin process is another method for producing butylene oxide, i.e., a butylene chlorohydrin process first with hypochlorous acid, followed by epoxidation. However, the production process of the chlorohydrin method needs to consume a large amount of chlorine, hypochlorous acid generated in the production process seriously corrodes equipment, and waste water and waste residue containing calcium chloride and organic chloride are generated, so that the environment is greatly polluted. The chlorohydrin process has been largely eliminated due to serious environmental pollution problems. The market demand of butylene oxide is continuously vigorous, so that the development of a butylene oxide production process which can be produced in large quantities and is environment-friendly and clean is urgently needed.
The cumene hydroperoxide method (CHP method) uses Cumene Hydroperoxide (CHP) as an oxidant, the CHP epoxidizes butylene to obtain epoxybutane and alpha, alpha-dimethyl benzyl alcohol, the alpha, alpha-dimethyl benzyl alcohol is hydrogenolyzed to generate cumene, and the cumene is oxidized to generate CHP for recycling. The process can directly produce the butylene oxide in large quantity, has simple flow, good catalyst stability, high purity of the butylene oxide product, no coproduct and basically no pollution, and is an environment-friendly atom economic type new green synthesis process of the butylene oxide.
The hydrogen peroxide oxidation method (HPPO method) adopts hydrogen peroxide to catalyze epoxidation of butylene to prepare epoxybutane, and the production process mainly generates epoxybutane and water, so that the process flow is simple, the product yield is high, other co-products are not generated, basically no pollution is caused, and the method is an environment-friendly novel clean production process.
Compared with a method for recovering butylene oxide from a propylene oxide byproduct and a chlorohydrin method, the CHP method and the HPPO method can be used for producing butylene oxide in large scale and in batches, the yield can be adjusted according to market demands, and the butylene oxide product has higher purity and better quality; the production flow is shorter, the waste water amount is greatly reduced, and no waste residue is generated. The advantages of environmental protection and cleanness of the two new methods are more suitable for the strategic requirements of national sustainable development.
The butylene oxide composition produced by CHP method and HPPO method comprises one or more compounds selected from water, propionaldehyde, acetone, butyraldehyde, isobutylene oxide, methanol, formic acidMethyl ester, C5～C8Impurities of hydrocarbons and mixtures thereof, wherein the impurities, with the exception of water and propionaldehyde, are not present in the chlorohydrin process and must be removed. At present, the national standard of the butylene oxide product is not yet established, and the impurities and the content of the product are not unified.
The invention patents CN104230856A, CN104098532A and CN104177314A disclose production methods for preparing epoxybutane by adopting a CHP method, the invention patents CN104003960A, CN104098531A and CN104311512A disclose process methods for preparing epoxybutane by adopting an HPPO method, and the epoxybutane products obtained by adopting the two methods contain water, hydrocarbons, methanol, propionaldehyde, acetone, butyraldehyde and other oxygen-containing compounds besides target products of the epoxybutane. The invention patents US4402794, JPS5646874 and CN103772325A disclose that the butylene oxide product is obtained by separation and purification in the manners of azeotropic distillation using water as solvent, extractive distillation using alkane as extractant, extractive distillation using high boiling point organic solvent such as sulfolane as extractant, etc., to remove impurities, and finally refined.
Although both the propylene oxide by-product butylene oxide and the chlorohydrin process can produce and/or purify butylene oxide compositions, such processes suffer from the disadvantages described above. Thus, there is a need for an environmentally clean process for producing butylene oxide compositions that does not rely on the chlorohydrin process.
Disclosure of Invention
The invention aims to solve the technical problems of long separation process, limited yield and low purity of butylene oxide recovered from the production process of propylene oxide in the prior art, and discloses a butylene oxide composition, in particular a butylene oxide composition prepared by a hydrogen peroxide isopropyl benzene method (CHP method), which has the advantages of wide raw material source, low cost, high product purity, green and environment-friendly process and suitability for producing polymers such as polyether polyol, foaming agent and the like.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: an oxetane composition comprising: at least 99.6 wt.% butylene oxide; and less than 2500wppm of epoxy isobutane.
In the above technical solution, preferably, the content of epoxy isobutane in the butylene oxide composition is less than 2000 wppm.
In the above technical solution, preferably, the content of isobutane oxide in the butylene oxide composition is less than 1000 wppm.
In the above technical solution, preferably, the content of isobutane oxide in the butylene oxide composition is less than 500 wppm.
In the above technical solution, preferably, the butylene oxide composition further comprises, in percentage by weight, less than 0.1 wt.% of water, methanol, methyl formate, propionaldehyde, butyraldehyde, and C5～C8At least one component of a hydrocarbon.
In the above technical solution, preferably, the butylene oxide composition further comprises less than 20wppm formic acid.
In the above embodiment, preferably, the butylene oxide composition further comprises less than 20wppm methyl formate.
In the above technical solution, preferably, the butylene oxide composition further comprises less than 30wppmC5～C8A hydrocarbon.
In the above technical scheme, when the butylene oxide is used for producing polyether polyol, especially for producing high-end polyether products, the content of aldehyde impurities directly affects the volatilization amount of organic matters in the polyether products, and the content of aldehyde needs to be strictly controlled, preferably, the butylene oxide composition further comprises less than 20wppm propionaldehyde and less than 20wppm butyraldehyde, and particularly preferably, the butylene oxide composition further comprises less than 20ppm of propionaldehyde and butyraldehyde.
In the above technical solutions, when the butylene oxide is used for producing the foaming agent, the water impurity content is critical to the foaming performance, and the water content needs to be strictly controlled, preferably, the butylene oxide composition further contains less than 80wppm of water, and particularly preferably, the butylene oxide composition further contains less than 50ppm of water.
In the above solution, preferably, the butylene oxide composition contains less than 32ppm water.
In the above technical scheme, the butylene oxide composition is obtained by refining crude butylene oxide, and the refining process comprises the following steps:
(1) the crude butylene oxide reacts with sodium hydroxide and hydrazine in sequence to decompose methyl formate, and most carbonyl compounds such as aldehyde, ketone and the like are reduced into hydrazone heavy components, and a crude butylene oxide solution after reaction is obtained at the same time;
(2) the reacted crude epoxy butane solution enters an extraction tower, and under the action of an extracting agent, water, methanol, residual aldehyde and ketone are removed by extraction and rectification, and simultaneously, the bottom liquid of the extraction tower is obtained;
(3) the bottom liquid of the extraction tower enters a separation tower, a crude product of the epoxybutane is obtained at the tower top after separation, and the bottom liquid of the separation tower containing the extractant enters a solvent recovery tower;
(4) refining the crude product of the butylene oxide in a product tower, and separating to obtain a butylene oxide composition at the tower bottom;
(5) and (3) feeding the bottom liquid of the separation tower containing the extracting agent into a solvent recovery tower, recovering the tower bottom to obtain the extracting agent after separation, and returning the extracting agent to the extraction tower for recycling.
In the above technical scheme, preferably, the crude butylene oxide contains, by weight, more than 95% of butylene oxide, and/or 300-5000 wppm acetone, and/or 300-5000 wppm propionaldehyde, and/or 300-5000 wppm butyraldehyde, and/or 300-8000 wppm epoxyisobutane, and/or 200-4000 wppm methanol, and/or 200-10000 wppm water, and/or 50-4000 wppm methyl formate, and/or 50-4000 wppm C5～C8A hydrocarbon.
In the above technical scheme, preferably, the crude butylene oxide is prepared by an epoxidation method.
In the above technical solution, preferably, the crude butylene oxide is prepared by Cumene Hydroperoxide (CHP) method, and the preparation of butylene oxide by the CHP method mainly comprises three reactions: cumene peroxidation, butene epoxidation and hydrogenolysis of alpha, alpha-dimethylbenzyl alcohol.
In the above technical scheme, preferably, the catalyst used in the butene epoxidation reaction is titanium-containing mesoporous or macroporous silica catalytic material Ti-HMS, Ti-TUD, Ti-MCM, Ti-KIT or Ti-SiO2。
In the above technical solution, preferably, the extractant is C7～C14Of (2) a hydrocarbonOne or more of the above classes.
In the above technical solution, preferably, the extractant is 2-methylheptane and/or n-octane.
In the above technical scheme, preferably, after the crude butylene oxide is added with alkali such as sodium hydroxide, the pH value of the solution is controlled to be 7.0-7.5, the reaction temperature is 30-60 ℃, the reaction time is 30-60 min, and the reaction pressure is 0.4-0.6 MPaG.
In the technical scheme, preferably, the molar ratio of the added hydrazine to the aldehyde such as the propionaldehyde in the crude butylene oxide is more than 1.0-1.5: 1, the reaction temperature is 30-60 ℃, the reaction time is 30-60 min, and the reaction pressure is 0.4-0.6 MPaG.
In the technical scheme, preferably, the number of tower plates of the extraction tower is 50-100, the operating pressure is 120-200 kPa, the operating temperature of a tower kettle is 80-150 ℃, the reflux ratio is 10-100, and the solvent ratio is 5-8; the number of tower plates of the separation tower is 40-90, the operating pressure is 100-180 kPa, the operating temperature of a tower kettle is 90-180 ℃, and the reflux ratio is 1-20; the number of tower plates of the product tower is 60-150, the operating pressure is 120-200 kPa, the operating temperature of a tower kettle is 60-120 ℃, and the reflux ratio is 60-150; the theoretical plate number of the solvent recovery tower is 10-80, the operation pressure is 80-150 kPa, the operation temperature of the tower kettle is 80-150 ℃, and the reflux ratio is 70-140.
Due to the presence of branched chains, the butylene oxide isomer is not beneficial to forming long chains in the polymerization process, has great influence on the polymerization, and needs to be strictly controlled to have the content of the isomer being less than or equal to 0.2 wt%, and preferably, the content of the isomer being less than or equal to 0.1 wt%.
In the above technical solution, the use of the butylene oxide composition for producing polyether polyols.
In the above technical solution, the use of a butylene oxide composition for the production of a blowing agent.
The invention relates to a process for producing a butylene oxide composition by a CHP method. The process for preparing the epoxybutane by the CHP method mainly comprises three reactions: cumene peroxidation, butene epoxidation and hydrogenolysis of alpha, alpha-dimethylbenzyl alcohol. Firstly, cumene and air are subjected to peroxidation reaction to generate Cumene Hydroperoxide (CHP), and the CHP and butylene are subjected to epoxidation reaction under the action of a titanium-containing mesoporous or macroporous silica catalyst to generate epoxybutane and alpha, alpha-dimethyl benzyl alcohol. In the presence of a special palladium/carbon catalyst, alpha-dimethyl benzyl alcohol and hydrogen undergo hydrogenolysis reaction to generate cumene, and the cumene returns to a peroxidation unit to be used as a raw material for preparing CHP for recycling.
The reaction temperature and pressure are important process parameters for the epoxidation reaction by adjusting the ring oxidation reaction temperature and pressure to maintain the overall conversion of CHP above 99%. Preferably, the epoxidation reaction is carried out under a liquid phase condition, the reaction temperature is 40-130 ℃, the reaction pressure is 1-8 MPa, and the molar ratio of the butene to the CHP is (1-20): 1, the space velocity of CHP is 1-15 h-1。
The process method is different from a crude epoxy butane composition produced in a chlorohydrin method production process, and the crude epoxy butane composition in the process contains methanol, propionaldehyde, acetone, butyraldehyde, epoxy isobutane, methyl formate and C5～C8Hydrocarbons and mixtures thereof. Preferably, the crude butylene oxide is separated to remove impurities and recovered to provide a butylene oxide composition.
In one embodiment, the present invention relates to a butylene oxide composition comprising butylene oxide and water, substantially free of cumene and acetone. Preferably, the butylene oxide composition comprises at least 99.5 wt.% butylene oxide, 5 to 200wppm water. The butylene oxide composition may also contain less than 0.1 wt.% of one or more organic impurities. These impurities may include, for example, propionaldehyde, butyraldehyde, isobutane oxide, methanol, methyl formate, C5～C8Hydrocarbons and mixtures thereof. For example, the butylene oxide composition may contain less than 100wppm water, less than 20wppm propionaldehyde, less than 20wppm butyraldehyde, less than 20wppm methanol, less than 20wppm methyl formate, less than 30wppmC5～C8A hydrocarbon.
In another embodiment, the invention relates to an epoxybutane composition refined from crude epoxybutane produced by a Cumene Hydroperoxide (CHP) process comprising at least 99.5 wt.% epoxybutane and less than 2000wppm epoxyisobutaneAnd further comprising less than 0.1 wt.% of a compound selected from the group consisting of propionaldehyde, methanol, methyl formate, C5～C8At least one component of a hydrocarbon. Wherein propionaldehyde is less than 20wppm, butyraldehyde is less than 20wppm, methanol is less than 20wppm, methyl formate is less than 20wppm, and C is5～C8Hydrocarbons are less than 30 wppm. In all embodiments, the butylene oxide composition is substantially free of C3～C4Hydrocarbons, cumene and acetone.
One of the creative efforts of the present inventors is that the inventors found critical values of the components in the butylene oxide composition affecting the subsequent applications of the butylene oxide composition, and when the content of the components is more than the critical value, the butylene oxide composition needs to be treated, thereby increasing the cost; when the content of the components is less than the critical value, the epoxy butane composition does not need to be processed and can be directly used for producing polyether polyol and foaming agent.
The butylene oxide composition prepared by the invention contains at least 99.6 wt.% of butylene oxide and epoxy isobutane with the volume of less than 2500wppm, and when the butylene oxide composition is used for producing polymers such as polyether polyol, a foaming agent and the like, the butylene oxide composition has the advantages of low raw material cost, high product purity and green and environment-friendly process.
Drawings
FIG. 1 is a schematic flow diagram of an embodiment.
In fig. 1, M1 is a mixer, M2 is a mixer, T1 is an extraction column, T2 is a separation column, T3 is a product column, T4 is a solvent recovery column, 1 is a crude butylene oxide feed, 2 is an alkali solution such as sodium hydroxide, 3 is a hydrazine solution, 4 is an extraction overhead stream, 5 is a product overhead stream, 6 is a butylene oxide composition, and 7 is a solvent recovery overhead stream.
The solution obtained after recovering butene and separating alpha, alpha-dimethyl benzyl alcohol from butene epoxidation product is crude butylene oxide, which mainly contains butylene oxide (the purity is generally more than 95 wt%), and impurities mainly comprise water, propionaldehyde, acetone, butyraldehyde, epoxy isobutane, methanol, methyl formate and C5～C8Hydrocarbons and mixtures thereof.
The crude butylene oxide 1 is soaped with sodium hydroxide 2 in a mixer M1 with methyl formateMethanol and sodium formate are generated by a chemical reaction, carbonyl compounds such as aldehyde and ketone are reduced into hydrazone substances in a mixer M2 with hydrazine 3, a crude butylene oxide solution after the reaction enters the lower part of an extraction tower T1, an extracting agent enters the upper part of the extraction tower, components such as water, methanol and residual aldehyde and ketone are removed by extraction rectification, a material flow at the bottom of the extraction tower enters a separation tower T2, a crude butylene oxide product is obtained at the top of the separation tower after the separation, a material flow at the bottom of the tower enters a solvent recovery tower T4, the crude butylene oxide product enters a product tower T3 to be refined, components such as isobutylene oxide are removed 5, a butylene oxide composition 6 is obtained at the bottom of the tower, a material flow at the bottom of the separation tower enters a solvent recovery tower, and C is5～C8And (4) returning the extractant obtained by recovering the hydrocarbon component 7 from the tower bottom to the extraction tower for recycling.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
Cumene and air are subjected to peroxidation reaction to generate Cumene Hydroperoxide (CHP), and the CHP and butylene are subjected to epoxidation reaction under the action of a Ti-HMS-containing catalyst to generate epoxybutane and alpha, alpha-dimethyl benzyl alcohol. In the presence of a special palladium/carbon catalyst, alpha-dimethyl benzyl alcohol and hydrogen are subjected to hydrogenolysis reaction to generate cumene, and the cumene returns to a peroxidation unit to be used as a CHP preparation raw material for recycling.
The reaction temperature of the epoxidation reaction is 100 ℃, the reaction pressure is 3MPa, and the mol ratio of the butylene to the CHP is 5: 1, the CHP space velocity is 5h-1。
The crude butylene oxide solution obtained after recovering butylene and separating alpha, alpha-dimethyl benzyl alcohol from butylene epoxidation product contains 97.3 wt% of butylene oxide, water, propionaldehyde, acetone, butyraldehyde, epoxy isobutane, methanol, methyl formate and C5～C8The total of hydrocarbon impurities was 2.7 wt%.
The butylene oxide composition is obtained by refining crude butylene oxide. The crude epoxy butane reacts with sodium hydroxide to decompose methyl formate, then reacts with hydrazine to reduce carbonyl compounds such as aldehyde and ketone into hydrazone substances, the crude epoxy butane solution after the reaction enters the lower part of an extraction tower, an extractant enters the upper part of the extraction tower, and extraction is carried outRectifying to remove water, methanol, residual aldehyde, ketone and other components, separating the bottom material flow in a separation tower, separating to obtain crude product of epoxy butane at the top of the separation tower, recovering the bottom material flow in a solvent recovery tower, refining the crude product of epoxy butane in a product tower, removing components of epoxy isobutane and the like, obtaining epoxy butane composition at the bottom of the separation tower, recovering the bottom material flow in the solvent recovery tower, and removing C at the top of the separation tower5～C8And (4) returning the extractant obtained by recovering the hydrocarbon components from the tower bottom to the extraction tower for recycling.
Wherein the extractant is 2-methylheptane, the theoretical plate number of the extraction tower is 60, the operating pressure is 140kPa, the tower kettle operating temperature is 104 ℃, the reflux ratio is 25, and the solvent ratio is 5.2; the theoretical plate number of the separation tower is 50, the operation pressure is 143kPa, the operation temperature of the tower kettle is 134 ℃, and the reflux ratio is 4; the theoretical plate number of the product tower is 80, the operation pressure is 136kPa, the operation temperature of the tower kettle is 78 ℃, and the reflux ratio is 100; the theoretical plate number of the solvent recovery tower is 30, the operation pressure is 100kPa, the operation temperature of the tower kettle is 124 ℃, and the reflux ratio is 95.
The product butylene oxide composition obtained using the above reaction and purification scheme contained at least 99.6 wt.% butylene oxide and less than 2000wppm isobutylene oxide, with the compositional data shown in table 1.
TABLE 1
| Butylene oxide composition component | Content (wt.) |
| Epoxy butane | ＞99.6wt％ |
| Propionaldehyde + butyraldehyde | 15ppm |
| Epoxy iso-butane | 1500ppm |
| Methanol | 15ppm |
| Formic acid methyl ester | 15ppm |
| C5～C8Hydrocarbons | 25ppm |
| Water (W) | 40ppm |
[ example 2 ]
The embodiment is the same as example 1.
Except that the epoxidation catalyst is Ti-KIT, the reaction temperature is 120 ℃, the reaction pressure is 3.5MPa, the mol ratio of the butylene to the CHP is 6:1, and the CHP space velocity is 4h-1。
The crude butylene oxide solution obtained by recovering butylene and separating alpha, alpha-dimethyl benzyl alcohol from butylene epoxidation product contains 95.7 wt% of butylene oxide, water, propionaldehyde, acetone, butyraldehyde, isobutylene oxide, methanol, methyl formate and C5～C8The total of hydrocarbon impurities was 4.3 wt%.
The butylene oxide composition is obtained by refining crude butylene oxide. Wherein the extractant is n-heptane, the theoretical plate number of the extraction tower is 70, the operation pressure is 160kPa, the operation temperature of the tower kettle is 120 ℃, the reflux ratio is 40, and the solvent ratio is 6; the theoretical plate number of the separation tower is 60, the operation pressure is 130kPa, the operation temperature of the tower kettle is 112 ℃, and the reflux ratio is 6; the theoretical plate number of the product tower is 100, the operation pressure is 150kPa, the operation temperature of the tower kettle is 81 ℃, and the reflux ratio is 90; the theoretical plate number of the solvent recovery tower is 35, the operation pressure is 120kPa, the operation temperature of the tower kettle is 110 ℃, and the reflux ratio is 95.
The product butylene oxide composition obtained using the above reaction and purification scheme contained at least 99.6 wt.% butylene oxide and less than 1000wppm isobutylene oxide, with the compositional data shown in table 2.
TABLE 2
[ example 3 ]
The embodiment is the same as example 1.
Except that the epoxidation catalyst is Ti-SiO2The reaction temperature is 110 ℃, the reaction pressure is 3.2MPa, the mol ratio of the butylene to the CHP is 8:1, and the space velocity of the CHP is 4.5h-1。
The crude butylene oxide solution obtained after butylene epoxidation product is subjected to butylene recovery and alpha, alpha-dimethyl benzyl alcohol separation contains 96.5 wt% of butylene oxide, water, propionaldehyde, acetone, butyraldehyde, isobutylene oxide, methanol, methyl formate and C5～C8The total of hydrocarbon impurities was 3.5 wt%.
The butylene oxide composition is obtained by refining crude butylene oxide. Wherein the extractant is n-octane, the theoretical plate number of the extraction tower is 65, the operation pressure is 150kPa, the operation temperature of the tower kettle is 117 ℃, the reflux ratio is 80, and the solvent ratio is 8; the theoretical plate number of the separation tower is 70, the operation pressure is 135kPa, the operation temperature of the tower kettle is 133 ℃, and the reflux ratio is 7; the theoretical plate number of the product tower is 120, the operation pressure is 145kPa, the operation temperature of the tower kettle is 83 ℃, and the reflux ratio is 110; the theoretical plate number of the solvent recovery tower is 40, the operation pressure is 115kPa, the operation temperature of the tower bottom is 127 ℃, and the reflux ratio is 90.
The product butylene oxide composition obtained using the above reaction and purification scheme contained at least 99.6 wt.% butylene oxide and less than 500wppm isobutylene oxide, with the compositional data shown in table 3.
TABLE 3
[ COMPARATIVE EXAMPLE 1 ]
Table 4 shows the chlorohydrin process and modified chlorohydrin process for producing butylene oxide compositions.
TABLE 4
| Butylene oxide composition component | Content (wt.) |
| Epoxy butane | ＞99.6wt％ |
| Propionaldehyde + butyraldehyde | ≤100ppm |
| Propylene oxide | ≤100ppm |
| Water (W) | ＞100ppm |
| Color intensity | ≤5 |
Example 1 epoxy butane composition and comparative example 1Similarly, but the impurity content in example 1 is generally lower than that in comparative example 1, and the impurity in comparative example 1 is propylene oxide, and methanol, methyl formate and C are not contained5～C8Hydrocarbons, and the like.
[ comparative examples 2 to 4 ]
The implementation mode is the same as that of the [ examples 1 to 3 ], except that mixers M1 and M2, a product tower T3 and a solvent recovery tower T4 are omitted, the top of a separation tower T2 is used for obtaining the epoxy butane composition (shown in tables 5 to 7), and an extracting agent obtained at the bottom of the tower is returned to an extraction tower for recycling.
TABLE 5
| Butylene oxide composition component | Content (wt.) |
| Epoxy butane | ＞99.5wt％ |
| Epoxy iso-butane | 7000ppm |
| Propionaldehyde + butyraldehyde | 70ppm |
| Methanol | 40ppm |
| Formic acid methyl ester | 120ppm |
| C5～C8Hydrocarbons | 70ppm |
| Water (W) | 150ppm |
TABLE 6
| Butylene oxide composition component | Content (wt.) |
| Epoxy butane | ＞99.5wt％ |
| Propionaldehyde + butyraldehyde | 100ppm |
| Epoxy iso-butane | 6000ppm |
| Methanol | 40ppm |
| Formic acid methyl ester | 100ppm |
| C5～C8Hydrocarbons | 100ppm |
| Water (W) | 200ppm |
TABLE 7
| Butylene oxide composition component | Content (wt.) |
| Epoxy butane | ＞99.5wt％ |
| Propionaldehyde + butyraldehyde | 60ppm |
| Epoxy iso-butane | 3000ppm |
| Methanol | 18ppm |
| Formic acid methyl ester | 80ppm |
| C5～C8Hydrocarbons | 20ppm |
| Water (W) | 70ppm |
After M1, M2, T3 and T4 are eliminated, the content of impurities in the epoxybutane composition is higher than that in [ examples 1-3 ], and the product quality is influenced when the epoxybutane composition is used for producing high polymer polymerization or surfactants. In addition, the extractant obtained from the separation tower contains impurities, and can be recycled without further impurity removal, so that impurity accumulation is caused, and the product purity of the epoxybutane composition is influenced.
[ example 4 ]
The polyether polyol, the polymer polyether polyol and the polytetramethylene ether glycol can be produced by the polyaddition reaction of epoxides such as butylene oxide and the like and initiators such as glycerol and the like under the action of a catalyst. The polymer polyol product TPOPB-43 produced by using the butylene oxide prepared in the example 1-3 as a raw material has the excellent performances of low content of organic volatile matters, high solid content, low viscosity and the like, and can be applied to manufacturing high-end furniture and high-end clothing foam.
[ COMPARATIVE EXAMPLE 5 ]
The epoxybutane prepared in the comparative examples 1 to 4 is used as a raw material, can be used for producing common polyether products such as low-foam polyether 210, high-foam polyether 4110 and the like, and is mainly applied to the fields of adhesives, building exterior wall heat preservation and the like, but the epoxybutane prepared in the comparative examples 1 to 4 cannot be used for producing high-end polyether products due to the fact that the content of aldehyde and water in the epoxybutane raw material is relatively high, and is low in economic utilization value.
[ example 5 ]
Polyether polyol generated by butylene oxide and isocyanate are taken as main raw materials, and the polyurethane foaming agent can be produced through the working procedures of mixing, foaming and the like under the action of a catalyst, a foam stabilizer and other auxiliary agents. The polyurethane foaming agent is filled in the pressure-resistant aerosol can, and when the materials collide out of the aerosol can, the foamed polyurethane materials rapidly expand and undergo a curing reaction to form foams. The cured foam has the effects of joint filling, bonding, sealing, heat insulation, sound absorption and the like. The epoxy butane prepared in the embodiment 1-3 is used as a raw material, can be used for producing SY8409 two-component polyurethane adhesive and FTC polyurethane insulation boards, and has the advantages of good decoration effect, strong bonding, shock resistance, pressure resistance, ultralow temperature thermal conductivity and the like when being used as building decoration materials.
[ example 6 ]
Cumene and air are subjected to peroxidation reaction to generate Cumene Hydroperoxide (CHP), and the CHP and butylene are subjected to epoxidation reaction under the action of a Ti-HMS-containing catalyst to generate epoxybutane and alpha, alpha-dimethyl benzyl alcohol. In the presence of a special palladium/carbon catalyst, alpha-dimethyl benzyl alcohol and hydrogen are subjected to hydrogenolysis reaction to generate cumene, and the cumene returns to a peroxidation unit to be used as a CHP preparation raw material for recycling.
The reaction temperature of the epoxidation reaction is 100 ℃, the reaction pressure is 3MPa, and the mol ratio of the butylene to the CHP is 5: 1, the CHP space velocity is 5h-1。
The crude butylene oxide solution obtained after recovering butylene and separating alpha, alpha-dimethyl benzyl alcohol from butylene epoxidation product contains 97.3 wt% of butylene oxide, water, propionaldehyde, acetone, butyraldehyde, epoxy isobutane, methanol, methyl formate and C5～C8The total of hydrocarbon impurities was 2.7 wt%.
The butylene oxide composition is obtained by refining crude butylene oxide. The method comprises the steps of decomposing methyl formate by reacting crude butylene oxide with sodium hydroxide, then reacting with hydrazine to reduce carbonyl compounds such as aldehyde and ketone into hydrazone substances, feeding the reacted crude butylene oxide solution into the lower part of an extraction tower, feeding an extracting agent into the upper part of the extraction tower, performing extractive rectification to remove components such as water, methanol and residual aldehyde and ketone, feeding the kettle material flow of the extraction tower into a separation tower, separating, and obtaining a crude butylene oxide product at the top of the separation tower, feeding the kettle material flow of the tower into a solvent recovery tower, feeding the crude butylene oxide product into a product tower for refining, removing components such as isobutylene oxide and the like, obtaining a butylene oxide composition at the bottom of the tower, feeding the kettle material flow of the separation tower into a solvent recovery tower, and removing C5～C8And (4) returning the extractant obtained by recovering the hydrocarbon components from the tower bottom to the extraction tower for recycling.
Wherein the extracting agent is 2-methylheptane and n-octane (weight ratio is 1: 1), the theoretical plate number of the extraction tower is 60, the operating pressure is 140kPa, the operating temperature of the tower bottom is 104 ℃, the reflux ratio is 25, and the solvent ratio is 5.2; the theoretical plate number of the separation tower is 50, the operation pressure is 143kPa, the operation temperature of the tower kettle is 134 ℃, and the reflux ratio is 4; the theoretical plate number of the product tower is 80, the operation pressure is 136kPa, the operation temperature of the tower kettle is 78 ℃, and the reflux ratio is 100; the theoretical plate number of the solvent recovery tower is 30, the operation pressure is 100kPa, the operation temperature of the tower kettle is 124 ℃, and the reflux ratio is 95.
The product butylene oxide composition obtained using the above reaction and purification scheme contained at least 99.7 wt.% butylene oxide and less than 1500wppm isobutylene oxide, with the compositional data shown in table 6.
TABLE 8
| Butylene oxide composition component | Content (wt.) |
| Epoxy butane | ＞99.7wt％ |
| Propionaldehyde + butyraldehyde | 10ppm |
| Epoxy iso-butane | 1200ppm |
| Methanol | 10ppm |
| Formic acid methyl ester | 10ppm |
| C5～C8Hydrocarbons | 20ppm |
| Water (W) | 30ppm |
[ COMPARATIVE EXAMPLE 6 ]
When the butylene oxide obtained in comparative examples 1 to 4 was used as a raw material, the water content was relatively high, and the foaming of the polyurethane foaming agent was too large and the size distribution was not uniform when the polyurethane foaming agent was produced. When the product is used for producing polyurethane composite boards and sound insulation boards, the problems of rough board surfaces, small cohesive force, poor sound insulation effect and the like exist.
Although the present invention has been described in detail, various modifications within the scope of the invention will be apparent to those skilled in the art. Furthermore, it is to be understood that various aspects of the invention, as well as various portions or all of various embodiments and features, recited below and/or in the appended claims, are combined or interchanged. In the description of the foregoing embodiments, references to another embodiment may be made in appropriate combination with other embodiments, as will be appreciated by those skilled in the art. Furthermore, those skilled in the art will recognize that the foregoing description is by way of example only, and is not intended to limit the present invention.
Claims (4)
1. An oxetane composition comprising, in weight percent: at least 99.6 wt.% butylene oxide; 125-1500 wppm epoxy isobutane; a total propionaldehyde and butyraldehyde content of 10-15 wppm; 10-15wppm of methanol; 10-15wppm methyl formate; 20-25 wppm C5～C8Hydrocarbons and 30-40 wppm water;
the butylene oxide composition is obtained by refining crude butylene oxide, and the refining step comprises the following steps:
(1) reacting the crude butylene oxide with sodium hydroxide and hydrazine in sequence to decompose methyl formate, reducing aldehyde and ketone carbonyl compounds into hydrazone heavy components, and obtaining a crude butylene oxide solution after reaction;
(2) the reacted crude epoxy butane solution enters an extraction tower, and under the action of an extracting agent, water, methanol, residual aldehyde and ketone are removed by extraction and rectification, and simultaneously, the bottom liquid of the extraction tower is obtained;
(3) the bottom liquid of the extraction tower enters a separation tower, a crude product of the epoxybutane is obtained at the tower top after separation, and the bottom liquid of the separation tower containing the extractant enters a solvent recovery tower;
(4) refining the crude product of the butylene oxide in a product tower, and separating to obtain a butylene oxide composition at the tower bottom;
(5) the liquid in the separation tower containing the extractant enters a solvent recovery tower, after separation, the tower kettle is recovered to obtain the extractant, and the extractant returns to the extraction tower for recycling;
the crude butylene oxide is prepared by an epoxidation method; the extractant is 2-methylheptane and/or n-octane; the reaction conditions in the step (1) are as follows: the molar ratio of hydrazine to aldehyde is greater than 1.0-1.5: 1, the pH value of the solution is 7.0-7.5, the reaction temperature is 30-60 ℃, the reaction time is 30-60 min, and the reaction pressure is 0.4-0.6 MPaG; the conditions of the steps (2) to (5) are as follows: the number of tower plates of the extraction tower is 50-100, the operating pressure is 120-200 kPa, the operating temperature of a tower kettle is 80-150 ℃, the reflux ratio is 10-100, and the solvent ratio is 5-8; the number of tower plates of the separation tower is 40-90, the operating pressure is 100-180 kPa, the operating temperature of a tower kettle is 90-180 ℃, and the reflux ratio is 1-20; the number of tower plates of the product tower is 60-150, the operating pressure is 120-200 kPa, the operating temperature of a tower kettle is 60-120 ℃, and the reflux ratio is 60-150; the theoretical plate number of the solvent recovery tower is 10-80, the operation pressure is 80-150 kPa, the operation temperature of the tower kettle is 80-150 ℃, and the reflux ratio is 70-140.
2. A butylene oxide composition according to claim 1, characterised in that the isobutylene oxide content is less than 1000 wppm.
3. A butylene oxide composition according to claim 2, characterised in that the isobutylene oxide content is less than 500 wppm.
4. Use of the butylene oxide composition of any of claims 1 to 3 to produce a polyether polyol and a blowing agent.
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| CN1714087A (en) * | 2002-11-26 | 2005-12-28 | 德古萨股份公司 | Process for the purification of crude propene oxide |
| CN103864723A (en) * | 2014-03-18 | 2014-06-18 | 中国石油集团东北炼化工程有限公司吉林设计院 | Technology for purifying epoxypropane |
| CN106397363A (en) * | 2015-08-03 | 2017-02-15 | 中国石油化工股份有限公司 | Purifying method for 1,2-epoxybutane |
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